The invention relates to flavouring and perfume compositions which contain one or more 3-alkyl-, 3-alkenyl- and 3-alkadienyl-substituted thiophenes and to foodstuffs and semiluxuries flavoured with one or more of these compounds or with said compositions and to products perfumed therewith. In addition, the invention relates to some 3-alkyl-, 3-alkenyl- and 3-alkadienyl-substituted thiophenes.
There is an on-going interest in the preparation of synthetic flavours and fragrances and the application thereof in foodstuffs and semiluxuries and in products to be perfumed such as cosmetics, soaps, detergents, household products and the like. This interest is stimulated by the insufficient quantity and often varying quality of natural flavours and fragrances. Although sulphur compounds per se generally do not have a pleasant taste and odour, it has nevertheless emerged that sulphur compounds play an essential role in many natural flavours and odours. It also appears that in many perfumes a somewhat "sulphurous" note is desirable to complete the total odour. There is therefore a requirement for compounds with a clearly pleasant sulphurous odour and flavour note which, however, does not come too strongly to the fore, preferably combined with other, pleasant olfactory properties so that the compounds can easily be combined with known fragrances and flavours.
Surprisingly, it has now been found that 3-substituted thiophenes with the general formula I ##STR2## have organoleptically very valuable properties, as a result of which they are very suitable for use as fragrances or flavours.
In formula I none, one or two of the dotted lines represents a double bond and in particular in a manner such that no cumulated double bonds are present. The compounds represented in this manner may have both the E and the Z configuration.
Such substituted thiophenes are hardly known in the perfume and flavour industry. U.S. Pat. No. 3,702,253 makes mention of 3-vinylthiophene which can be used as a flavour in foodstuffs and drinks and has a hydrocarbon-like odour or taste.
Said compound, however, has chemical structure quite a different the 3-(4-methylpentyl)thiophene, 3-(4-methylpentenyl)thiophene and 3-(4-methyl-pentadienyl)-thiophene of the present invention.
3-(4-Methylpent-3-enyl)thiophene has been detected by various investigators in hop oil (see A. Suggett, M. Moir, J. C. Seaton, Proceedings of the European Brewery Convention Congress, Berlin, 1979, pages 79-89; T. L. Peppard, J. A. Elvidge, Chem. & Ind. 1979, pages 552-3; S. Araki, Y. Butsugan, Bull. Chem. Soc. Japan, 56 (1983), pages 1446-9 and J. A. Elvidge, S. P. Jones, J. Chem. Soc. Perkin I, 1982, pages 1089-94). In the last publication the compound is described as a "pungent oil". Suggett and his coworkers, who first detected this and some other sulphur compounds in hop, report that they give an undesirable flavour when added to beer.
The other compounds according to the invention were hitherto unknown.
It was not possible to suppose therefore that the compounds according to the invention would have such valuable and varied organoleptic properties which, in addition to a general, but not very pronounced sulphurous note contain, inter alia, flowery, green, spicy, citrus-like, malty and caramel-like odour and taste notes. Thus, the above-mentioned 3-(4-methylpent-3-enyl)thiophene is characterized by a pleasant green and citrus-like odour and a taste which clearly has citrus aspects and the organolepsis of Z-3-(4-methylpenta-1,3-dienyl)thiophene exhibits a green and fresh-flowery character, but that of E-3-(4-methylpenta-1,3-dienyl)thiophene exhibits a spicy, malty, caramel-like character.
The compounds according to the invention can be used as such as flavours and fragrances, or they can first be mixed with suitable carriers or diluents. They can also be combined with other single compounds or with mixtures, for example with ethereal oils, in a usual manner for the formation of flavouring or perfume compositions. In this connection the terms "flavouring composition" and "perfume compositions" mean mixtures of flavours or fragrances respectively and/or ethereal oils, if desired dissolved in a suitable solvent or mixed with a powdered substrate or processed to form a powdered product and used to impart a desired taste or odour to products of all types, or to reinforce or to improve the taste or odour which these products already have. Products to be flavoured are foodstuffs and semiluxuries, by which in this connection are meant: solid or liquid products intended for human consumption, including tobacco products, medicines and toothpaste. Products to be perfumed are, for example, soaps, detergents, air-fresheners, room sprays, pomanders, candles, cosmetics such as creams, ointments, toilet waters, pre- and after-shave lotions, talcum powders, hair-care agents, body deodorants and antiperspirants.
Basic perfume and flavouring substances which can be advantageously combined with the compounds according to the invention are, for example, natural products such as extracts, ethereal oils, absolutes resinoids, resins, concretes, etc., but also synthetic basic substances such as hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, ketals, nitriles, etc., including saturated and unsaturated compounds, aliphatic, carbocyclic and heterocyclic compounds.
Such basic materials are mentioned, for example, in S. Arctander, Perfume and Flavor Chemicals (Montclair, N.J., 1969), in S. Arctander, Perfume and Flavor Materials of Natural Origin (Elizabeth, N.J., 1960) and in T. E. Furia et al., CRC Fenaroli's Handbook of Flavor Ingredients, 2nd edition (Cleveland, CRC Press Inc., 1975).
Examples of fragrances which can be used in combination with the compounds according to the invention are geraniol, geranyl acetate, linalol, linalyl acetate, tetrahydrolinalol, citronellol, citronellyl acetate, dihydromyrcenol, dihydromyrcenyl acetate, tetrahydromyrcenol, terpineol, terpinyl acetate, nopol, nopyl acetate, 2-phenylethanol, 2-phenylethyl acetate, benzyl alcohol, benzyl acetate, benzyl salicylate, styrallyl acetate, benzyl benzoate, amyl salicylate, dimethylbenzylcarbinol, trichloromethylphenylcarbinyl acetate, p-tert-butyl cyclohexyl acetate, isononyl acetate, vetiveryl acetate, vetiverol, .alpha.-hexylcinnamaldehyde, 2-methyl-3-(p-tert-butylphenyl) propanal, 2-methyl-3-(p-isopropylphenyl)propanal, 3-(p-tertbutylphenyl)propanal, tricyclodecenyl acetate, tricyclodecenyl propionate, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde, 4-(4-methyl-3-pentenyl)-3-cyclohexenecarbaldehyde, 4-acetoxy-3-pentyl-tetrahydropyran, 3-carboxymethyl-2-pentylcyclopentane, 2-n-heptyl-cyclopentanone, 3-methyl-2-pentyl-2-cyclopentenone, n-decanal, n-dodecanal, 9-decenol-1, phenoxyethyl isobutyrate, phenylacetaldehyde dimethylacetal, phenylacetaldehyde diethylacetal, geranyl nitrile, citronellyl nitrile, cedryl acetate, 3-isocamphylcyclohexanol, cedryl methyl ether, isolongifolanone, aubepine nitrile, aubepine, heliotropin, coumarin, eugenol, vanillin, diphenyl oxide, hydroxycitronellal, ionones, methylionones, isomethylionones, irones, cis-3-hexenol and esters thereof, indan musks, tetralin musks, isochroman musks, macrocyclic ketones, macrolactone musks, ethylene brassylate, aromatic nitromusks.
Auxiliary materials and solvents which can be used in perfume compositions which contain compounds according to the invention are, for example: ethanol, isopropanol, diethyleneglycol monoethyl ether, diethylphthalate etc. Such auxiliary materials and solvents for aroma compositions are, for example: ethanol, diethyleneglycol monoethyl ether, propylene glycol, glycerol and triacetin.
The quantities of the compounds according to the invention to be used may be strongly divergent and depend, inter alia, on the product in which the compounds are used and on the nature and the quantity of the other components of a flavouring or perfume composition.
In most cases a quantity of 0.05 parts by weight per million of a compound according to the invention in foodstuffs and semiluxuries will already be perceptible. In concentrated flavouring compositions a quantity of up to 5% by weight can be used with advantage in some cases.
In concentrated perfume compositions quantities of 100 parts by weight per million may already have a perceptible effect on the odour impression. On the other hand, to achieve special odour effects it is also possible to use a quantity of 5% by weight or even more in a composition. In products perfumed with the aid of perfume compositions these concentrations are proportionally lower, depending on the quantity used of the composition in the finished product.
The compounds according to the invention can be prepared according to methods usual for such compounds, for example by the Wittig reaction of 3-thienylcarbaldehyde or 3-thienylacetaldehyde with an ylide prepared from a suitably chosen alk(en)yltriphenylphosphonium halide. Insofar as it is possible for the compounds according to the invention to be (Z)- and (E)-isomers, the above-mentioned synthesis methods yield a mixture of said isomers. The ratio of isomers in the mixture can be influenced by changes in the reaction procedure. Thus, more of the (Z)-isomer is obtained if the reaction is carried out in a nonpolar solvent and, on the other hand, more of the (E)-isomer is obtained in polar solvents and/or in the presence of lithium salts, for example by making use of a lithium base for the preparation of the ylide. The Wittig reaction is described in J. March, Advanced Organic Chemistry, 2nd edition, pages 864-872, in particular page 870, and in the literature mentioned therein.
The 4-methylpentyl and some 4-methylpentenyl copounds may be prepared by a Wurtz-type reaction between 3-halomethylthiophene, a 3-methylbut(en)yl halide and magnesium.
3-(4-Methylpent-3-enyl)thiophene can be prepared according to the instructions of S. Araki and Y. Butsugan (see above) or of A. Corvers, J. H. van Mil, M. M. E. Sap and H. M. Buck, Rec. Trav. Chim. Pays BAS, 96 (1977), pages 18-22.
Isomeric mixtures obtained in the preparation of compounds according to the invention may be separated into the separate isomers in a conventional manner, for example by means of preparative GLC. As a rule, however, such a separation is not necessary and the isomeric mixture can be used with advantage as a flavouring or perfume.
The following examples are exclusively intended to illustrate the method according to the invention and the synthesis of the compounds according to the invention. The invention is, however, not limited thereto.